Fluorescent compound and methods of imparting fluorescent effects to materials



Patented June 23, v 1953 FLUORESCENT-y COMPOUND AND METHODS OF IMPARTINGFLUORESCENT EFFECTS TO MATERIALS Leslie Noel Savidge and Richard Thomas,Bromborough, England, assignors to Lever Brothers Company, Cambridge,

Maine Mass., a corporation of No Drawing. Original application March 30,

1948, Serial No. 18,066. Divided and this application August 13, 1949,Serial No. 110,223. In Great Britain April 3, l94-7 This inventionrelates to methods of treating materials with blue-fluorescentsubstances so as to impart to the materials blue-fluorescent; effects,with or without detergents. The invention also relates to newblue-fluorescent-agents suitable for use with these methods, includingdetergent containing compositions.

The present invention is particularly concerned with the treatment ofmaterials, such as, for example, 1 textiles, with fluorescent substanceswhich, without substantially altering the color. of the treatedmaterial, are capable of imparting to it a blue fluorescence, that is, afluorescence in which at least a major part of the absorbed light in theviolet end of the spectrum is re-emitted within the blue portion of thespectrum.

a The present invention is based on the discovery of new chemicalcompounds which are substantive and which impart fluorescent effects tomaterials,such as textiles; which effects have good stability, not onlyto air and light, but also to sodium hypochlorite and similar bleachingagents; and the said compounds are therefore particularly useful forimparting fluorescent effects to materials which may be subjected to 16Claims. (c1. iii-33.5)

new articles made therefrom, or in the washing or rinsing of sucharticles including soiled articles. As the compounds are substantive tocellulosictextile fibres, the whitening effect produced is of a more orless permanent nature and will survive-many ordinary washing or rinsingtreatment with hypochlorite or the like. I Such treatments are used, forexample, .in the bleaching of textiles or in the laundering of whitearticles for improving a the color or removing fruit, tea, coffee andsimilarstains which are not 'removed by the normal washing process.

The invention comprises a method'of imparting to materials, particularlycotton, linen, rayon and other cellulose materials, blue fluorescenteffects by incorporating in the said materials: a small proportion of anew compound as described; hereinafter. The invention also providespreparations comprising substances such as detergents, starch and othersubstances and' containing small proportions of the said new compound.In addition, the invention provides'methods of in'-' corporating thenew'compoundsin textilesan'd the like materials, e. g.,- in the presence ofa detergent.

The incorporation of the compounds in textiles and textile articles maybe carried out by im"- mersing the articles in an aqueous solution ofthe compound. It is found, however, that in corporation is oftenmaterially 'assisted 'by the presence of small percentages (usuallyquantities below 1% are sufficient) of electrolytes such as sodiumcarbonate, sodium sulfate or sodium chloride. The process of theinvention may ad.-' vantageously be applied to textiles in any stage oftheir manufacture or subsequently, that is to' say to the yarn, to thenewly woven fabric, to

treatments.

The substances which are employed in accordance with the invention havethe following general formula:

in'which each R and R1 is a hydrocarbon radical,- such as alkyl, aryl,or aralkyl, lower alkyl of from 1 to 4 carbon atoms being preferred;each :0 and am being zero or a small integer such as 1, 2v or 3, or thelike; each n, m being integers expressing the number of the respectivegroups substituted in the benzene rings, such as l, 2, 3, and the like(the maximum number being the positions on the benzene rings which arenot otherwise substituted) each 172, m1 being integers expressing thenumber of groups substituted in the terminal benzene rings, such numberbeing at least 2 and not more than the number of positions on thebenzene rings which are not otherwise substituted; B being hydrogen or acation such as sodium, potassium, ammonium, or the like. The compoundsshould not contain any free (primary) amino groups directly attached toany benzene ring, since the presence of such groups renders thecompounds unstable to light, air and oxygen;"= Any of the benzene ringsmay contain siibstituents (except as specified above), such as methyl,acetylamino, and the like.' Salts, such as sodium salt," are mostconvenient to use in practice.

In a preferred embodiment the compounds have the formula (0 R)2 or 3 CHNHCO 0,11 GHQ-b11300 (0 1): or a ing compounds are illustrative:

3 COMPOUND No. 1

Sodium N :N-bis-(3-4-dimethoxybenzoyl) 4:4-

diaminostiZbene-Z:2-disulfonate orno c OHNQOH=C HONHC G0 om 6on3 SO Nasome 0 on.

COMPOUND NO. 2

Sodium N :N '-bis- (3 :4:5-trz'methoa:ybenzoyl) 4 :4 -diaminostilbene-2:2 -disul,f.onate CH3? con. CHaO CONH CH=CH NHCO 0cm Any of the abovecompounds may be prepared by reacting 4 :4-diaminostilbene-22'-disulfonic acid with the corresponding acyl chloride and in thepresence of suflicient sodium carbonate to render the mixture alkaline.For instance, in the case of Compound No. 1,meta-para-di-methoxybenzoyl-chloride in pyridine is added during aperiod of a few minutes and the mixture heated under reflux for onehour. The mixture is heated once again with sodium carbonate and cooled.The product was collected by filtration and washed with water. Thematerial may be purified by dissolving in hot aqueous pyridine,decolorized and filtered. On cooling the product crystallized which canbe washed with water and dried.

Compound No. 2 can be prepared in a similar manner except that3,4,5-tri-methoxybenzoyl chloride is used as the reagent for introducingthe appropriately substituted benzoyl group.

The following examples illustrate the invention and are applicable toany of the compounds described.

EXAMPLE I Undyed bleached cotton yarn is treated in an aqueous bathcontaining 0.14% of sodium sulfate and 0.005% of the blue-fluorescentcompound.

The treated yarn after rinsing and drying has 8.

brilliant white appearance in daylight, and shows strong bluefluorescence when illuminated by ultra-violet light and remains stronglyfluorescent after long exposure to daylight and ultra-violet light.

EXAMPLE II A new white cotton cloth is rinsed for a few minutes in anaqueous bath containing 0.005% of the blue-fluorescent compound. Thetreated cloth after drying and ironing shows a brilliant whiteappearance in daylight, which is not affected when the cloth issubsequently treated with a dilute solution of hypochlorite.

EXAMPLE III ing soiled cotton cloths with a wash liquid containing soappowder and the blue-fluorescent compound, in a manner similar to theforegoing; even in the first washing, and the effect improves withsubsequent washings.

The requisite amounts of aminostilbene compounds in the washing liquoror in the preliminary laundering treatment may vary within wide limits.In general, it is preferred to express this in terms of the amount oftextile to be treated, and usually not over about 0.01% is necessary,based on the dry weight of the textile material to be washed.Proportions ranging from 0.025 to 0.001% have been found sufllcient toimpart an appreciable whitened eil'ect. There is no advantage in usingmore than is necessary to obtain the white effect and, of course, theamounts used should be less than sufllcient to impart a colored efiectthereto. The amount need not be larger than 0.05%, based on the textilematerial to achieve a satisfactory whitening efiect. Higher amountsusually serve no useful purpose once the quantity producing maximumwhitening effect for a given case has been reached.

If the detergent composition contains 0.01 to 0.075% by weight of theaminostilbene compound and the washing liquor contains 0.25 to 0.75% byweight of the detergent composition, the concentration in the liquor ofthe aminostilbene compound can be readily calculated.

The compounds of the present invention are particularly suitable for usein starch preparations for imparting fluorescent effects to materialssuch as textiles and the like.

EXAMPLE IV A solution containing 200 cc. of water, 0.01 g. of theblue-fluorescent compound, '1 g. of sodium sulfate, and 20 g. of goodquality maize starch-is suspended in solution at 40 C. for 30 minutes,filtered ofi and dried at 40 C. The treated starch is very much whiterthan the original starch. An improvement in the whiteness of starch isalso obtained by using only onetenth of the above quantity of thecompound in EXAMPLE V A new white cotton cloth is treated with anaqueous solution containing 0.01% of the bluefluorescent substance and0.004% of ultramarine. A brilliant white appearance is imparted to thecloth, which is considered by some observers to be preferable in tone tothat obtained by the use of the blue-fluorescent substance alone.

It will be realized that a preparation can be made, in accordance withthe invention, comprising a blue-fluorescent substance of the generalformula mentioned above, and a blueing agent, that is a blue-coloredsubstance such as is used in the normal blueing treatment for washedtextile articles, Such'a preparation may also contain starch, and anyfillers and other substances such as are incorporated in blueing agents.

In this connection, it may be mentioned that to a certain extentwhiteness is a subjective impression of the observer. Shades of whiteexist, for example a bluish white, a greenish white or a pinkish white;and while one observer may consider a bluish White to be the whiter ofsamples of the three shades, another observer may prefer the greenershade. The incorporation of a small amount of colored substance with theblue-fluorescent compound enables any desired shade of white to be givento the material to which'the blue-fluorescence is imparted, and anysuitable colored substance or dye may be so incorporated.

Thus the mixture of a blue-fluorescent substance and a suitable dye orpigment in the requisite proportions, together with any filling agentsmay be formed into a useful preparation for the purposes of theinvention.

The compounds of the present invention may usefully be incorporated indetergents, in any form such as bars, tablets, powders, flakes. Theincorporation in soap powder has already been mentioned above in ExampleIII. In this way, a detergent is provided which simultaneously washesand Whitens materials to which it is applied.

The detergents that are used with the stilbene such as the Turkey redoil of commerce, alkylv sulphates such as sodium lauryl sulfate(Gardin01) aliphatic sulfonates such as the condensation product ofoleoyl chloride with the sodium compound are of the kind suitable forand cus- Q O Q sation product of oleoyl chloride with the sodium salt oftaurine (Igepon T), diamyl sodium sulfosuccinate, alkyl aryl sulfonatessuch as the sodium salt of an alkyl benzene or naphthalene sulfonateacid wherein the alkyl group contains about 8 to 18 carbon atoms(Nacconol) Twitchell reagents, quaternary ammonium compounds such ascetyl trimethyl ammonium chloride, partial esters of polyhydricalcohols, such as mono stearin sodium sulfo acetate, sodium glycerylmonolaurate sulfate (Syntex M), dioctyl' sodium sulfosuccinate (AerosolOT), sapamines, pentaerythritol monostearate (Pentamul 6), polyglycolesters, and the like (as are known in the art, for instance, Bailey,Industrial Oil and Fat Products, Interscience Publishers, Inc., NewYork, N. Y., 1945, chapter XII; and Dean, Utilization of Fats, ChemicalPublishing Company of New York, Inc., New York, N. Y., 1938, chapter IX,part 5) In the textile industry the compounds have use in theirapplication to piece goods, yarns, fibre, fabrics and articles such asshirts, towels, sheets and the like made therefrom. Such materials maybe treated with a dilute aqueous solution of the substance, whichbecomes attached to the material, giving it a brilliant whiteappearance, which, owing to the substantive properties of the substance,will remain through many normal washing and rinsing operations, thusremoving the necessity for special blueing or whitening treatments eachtime the material is laundered.

Among other useful applications of the invention may be mentioned thepreparation of fluorescent inks for marking textile fabrics to becleaned or laundered with identification marks which are normallyinvisible but strongly fluorescent in ultra-violet light. It is clearlyessential that such identification marks withstand customary launderingtreatments and in particular do not become discolered when, for example,hypochlorite is used in the wash or the fabrics are dried in the sun,since any discoloration would obviously be highly detrimental.Identification marks produced by means of the blue-fluorescent compoundsaccording to the invention remain practically unaffected by normallaundering operations.

The invention is not limited to the applications specifically referredto in this specification, but is useful for any purpose to whichlight-stable blue-fluorescent substances may be applied, except as isnot within the scope of the appended claims.

This application is a division of our application Serial No. 18,066filed March 30, 1948.

We claim:

1. A compound of the general formula 2. A compound of the formula:

I OR

BOaNa in which R is an alkyl radical having 1 to 4 salt of isethionicacid (Igepon A), the condencarbon atoms.

son;

in which B is selected from the group consisting of hydrogen, sodium,potassium and ammonium; and R is an alkyl radical having one to fourcarbon atoms.

4,4,4; bis (3,4 dimethoxy benzoylamino) -stilbene-2,2-disodiumsulfonate.

5. A method of laundering textile material which comprises washing saidmaterials with an aqueous solution comprising water and a detergentcomposition consisting essentially of a detergent comprising an organicdetergent and about 0.01% to about 0.075% by weight of a compound ofclaim 3.

6. A method of laundering textile material which comprises Washing saidmaterials with an aqueous solution comprising water and a detergentcomposition consisting essentially of a detergent comprising an organicdetergent and about 0.01% to about 0.075% by Weight of acompound ofclaim 2.

7. A method of laundering textile material which comprises washing saidmaterials with an aqueous solution comprising Water and a detergentcomposition consisting essentially of a detergent comprising an organicdetergent and about 0.01% to about 0.075% by weight of a compound ofclaim 1.

8. A composition consisting essentially of a detergent comprising anorganic detergent and not more than about 0.075% by weight of a compoundof claim 3.

9. A composition consisting essentially of aby weight of a- 11. Acomposition :consisting essentially of an organic detergent comprising asoap and not more than about 0.075% by weight of a compound of claim 1.

12. A composition consisting essentially of-an organic detergentcomprising a synthetic organic nonsoap detergent and not more than about0.075% by weight of a compound of claim 1.

13. A method of imparting blue-fluorescent effects to materials whichcomprises immersing said materialsin an aqueous'solution containing fromabout 0.0001 to about 0.05% by weight, calculated on the basis of thedry weight of materials treated, of a compound of claim 3, removing saidmaterials from said solution and'drying said materials.

14. The method of claim 13 in which the material treated is a fibrouscellulosic material.

15. Fibrous cellulosic material having incorporated therein about0.0001% to about 0.05% by weight of a compound of claim 3. 1

16. Fibrous cellulosic material having incorporated therein about0.0001% to about 0.05% by Weight of a compound of claim 1. I Y

LESLIE NOEL SAVIDGE. RICHARD THOMAS.

.References Cited in the file of this patent UNITED STATES PATENTS OTHERREFERENCES Serial No. 381,856 (A. P. c. 11,1943.

published May 7

1. A COMPOUND OF THE GENERAL FORMULA
 16. FIBROUS CELLULOSIC MATERIALHAVING INCORPORATED THEREIN ABOUT 0.0001% TO ABUTT 0.05% BY WEIGHT OF ACOMPOUND OF CLAIM 1.